Heterocyclic Annelated Di(perylene bisimide): Constructing Bowl-Shaped Perylene Bisimides by the Combination of Steric Congestion and Ring Strain

In this paper, we present the synthesis of S- and N-heterocyclic annelated di(perylene bisimide) With extraordinary doubly bowl-shaped structures. The structures of fused PBI bowls confirmed by single-crystal X-ray structure analysis and temperature-dependent H-1 NMR are realized by the introduction of the steric congestion in nonbay regions and by the concurrent formation of the five-membered heterorings strain in bay regions. On the basis of the geometry obtained from the X-ray analysis, the maximum POAV1 pyramidalization angle is found in N-heterocyclic annelated diPBI 7, as large as 4.7 degrees. indicating the formation of two PBI bowls with significant curvatures. Furthermore, to assist the electrochemical and spectroscopic characterization of the two bowl-shaped derivatives and to assess the influence of heteroatoms on the bowl curvature, quantum-chemically optimized atomic structure, electronic properties, and optical signatures were computed with density functional theory.